KR100898500B1 - A production method of aminated sorbent - Google Patents

Abstract

The present invention relates to a method for preparing an adsorbent in which an amine group is present as a functional group on a silica surface, and more particularly, a mixture in which a silica mixture (A) formed by mixing silica and an organic solvent and a substance (B) having an amine group are mixed. The adsorbent prepared through the step and the filtered mixture is heated at a predetermined temperature to react the amine group with silica and then filtered and washed to have a high adsorption rate for carbon dioxide, and the adsorption rate of carbon dioxide at different temperatures is different. It is higher than the physical adsorbent, and relates to a method for preparing an adsorbent having an amine functional group which can be used for separating carbon dioxide from the exhaust gas of a carbon dioxide generating process such as a thermal power plant, a steel mill, and a fermentation process.

Silica, organic solvent, functional group, carbon dioxide, separation, amine, adsorption, absorption

Description

A method for producing an adsorbent having an amine functional group {A PRODUCTION METHOD OF AMINATED SORBENT}

The present invention relates to an adsorbent having an amine functional group using adsorption and absorption processes among carbon dioxide separation methods, which are greenhouse gases which have the greatest influence on global warming.

Recently, the methods proposed for the reduction and treatment of carbon dioxide have been proposed as absorption, adsorption, and membrane separation as a separation process after combustion, and there is a decarbonization method as a separation process before combustion.

In the post-combustion separation, absorption is a method of absorbing and separating carbon dioxide using an amine-based absorbent, and decomposing the carbon dioxide combined with the amine by heat to desorb it at high concentration. At this time, a large amount of energy is required in the separation process, it is essential to purify the amine used. Therefore, since the process becomes very complicated, the equipment and equipment cost can be said to be the highest among the existing methods of separating carbon dioxide. Therefore, it is advantageous to separate from large source, but the application to small source is separated. In addition, the method of using a high temperature dry absorbent (Korean Patent Registration No. 10-0550209 (notified date 2006.02.08)) has the advantage of directly obtaining a high concentration of carbon dioxide in the separation process of carbon dioxide and a dry absorbent, Loss has a big disadvantage. In addition, in the case of the membrane separation method, the currently manufactured membrane price is very high, the equipment cost of the pretreatment device for purification of the combustion gas is very high, and the replacement cost due to the contamination of the membrane is very high. In the case of the adsorption method, the current method is to use pressure change and temperature change, and sometimes the separation process is operated by changing the pressure and temperature at the same time. At this time, the adsorbent used is mainly zeolite molecular sieve, activated carbon, carbon molecular sieve. In the case of zeolite molecular sieve, the adsorption efficiency is high, but it causes problems due to contamination by other components contained in the combustion gas, and in the case of activated carbon, the adsorption amount is lower than that of zeolite.

Therefore, in order to increase the adsorptive separation efficiency of carbon dioxide, most of them are operated at a high pressure, and the high concentration of carbon dioxide cannot be separated during the separation process, thereby separating the high concentration of carbon dioxide through many steps. In addition, the carbon dioxide adsorption amount of the adsorbent is greatly influenced by the temperature, so the cooling process is performed to supply a low temperature before the separation process, and water separation is essential because the amount of adsorption by water is largely reduced. Therefore, such a conventional driving method and constraints require a lot of power costs, there is a problem that it is difficult to increase the size.

In order to solve the above problems, the present invention has a small or no decrease in the amount of adsorption of carbon dioxide by moisture, is higher than the operating temperature of other physical adsorbents, and is a temperature after passing the apparatus for removing polluted gas by exhaust gas regulation. It aims to produce a new concept of adsorbent which shows high adsorption amount at 50-80 ° C and desorption of carbon dioxide at 110 ° C or lower.

Another object is to provide an adsorbent that can treat carbon dioxide at a high concentration in the source of carbon dioxide.

Another object is to provide an adsorbent that can compensate for the disadvantages of the adsorbents listed above and increase the adsorption efficiency.

In order to achieve the above object, the present invention is a silica mixture (A) 90 to 99% by weight of a mixture of 0.2 to 50% by weight of silica and 50 to 99.8% by weight of an organic solvent, and a material having an amine group (B) A mixing step of mixing 1 to 10% by weight,

The main technical configuration of the adsorbent manufacturing method having an amine functional group is a mixture of the mixture passed through the heating step at 40 ~ 170 ℃ heated to react the amine group with silica and then filtered and washed.

Hereinafter, the technical configuration of the adsorbent manufacturing method having the amine functional group will be described in detail.

First, 0.2 to 50% by weight of silica is placed in 50 to 99.8% by weight of organic solvent, and silica is made by dispersing the organic solvent into the pores of silica using vacuum to remove air and wet the organic solvent on all silica surfaces. 1 to 10% by weight of the substance (B) having an amine group is added to 90 to 99% by weight of the mixture (A).

The silica of the silica mixture (A) is a mesoporous silica having a specific surface area of 900 to 1,020 m 2 / g dried by vacuum drying, and having an average particle diameter of 3 nm, and when used in less than 0.2% by weight, grafting of amine groups is performed. Since there is a problem of less, and when used in excess of 50% by weight, there is a problem of reduction in efficiency due to unreacted amine, it is preferable to use the silica in the range of 0.2 to 50% by weight.

The organic solvent of the silica mixture (A) is any one or two or more selected from toluene, benzene, xylene, hexane, ether, and when used in less than 50% by weight is not sufficient diffusion, 99.8% by weight In the case where it is used in excess, there is a problem that it takes a very long time to penetrate the amine group inside the pores, it is preferable to use the organic solvent 50 ~ 99.8% by weight.

The substance (B) having the amine group is any one or more selected from aminopropyltrimethoxysilane, aminopropyltriethoxysilane and aminopropyl chloride, and has a amine group in the silica mixture (A). After the addition of (B) is completed, the mixture is stirred for 5 to 7 hours in a nitrogen or argon atmosphere without contact with air at room temperature.

In this case, when the silica mixture (A) is used at less than 90% by weight, there is a problem in efficiency reduction due to unreacted amine groups, and when used in excess of 99% by weight, the amine group is insufficient in the amine group grafting process, so that the complete amine Since there is a problem that the group grafting is not possible, the silica mixture (A) is preferably used 90 to 99% by weight, and the amine group is insufficient even when the material (B) having the amine group is used in less than 1% by weight There is a problem, and when used in excess of 10% by weight, there is a problem that the washing process of the unreacted amine group is more complicated, it is preferable to use the material (B) having the amine group in the range of 1 to 10% by weight. Do.

After the stirring is completed, the mixture is stirred and heated for 10 to 15 hours at atmospheric pressure above the evaporation temperature of the organic solvent using a reflux apparatus to react with hydroxyl groups and ethyl groups on the silica surface to produce ethyl alcohol, methyl alcohol, hydrochloric acid, and Silicon and aminosilane silicon react with each other.

After the reaction is completed, unreacted aminosilane and toluene are filtered and washed with any one or more organic solvents selected from methyl chloride, ethyl alcohol, and ether. In order to remove the unreacted product and the reaction product, the mixture was stirred and heated for 3 to 5 hours using ethyl alcohol in a reflux apparatus, and the unreacted aminosilane and toluene were any one or more selected from methyl chloride, ethyl alcohol and ether. Filtration and washing with an organic solvent, and drying in a dryer for 10 to 14 hours at 90 ~ 120 ℃ to complete the preparation of the adsorbent.

As described above, the adsorbent prepared by the method for preparing the adsorbent having the amine functional group of the present invention may be manufactured and used in the form of honeycomb, monolith bed, or bead, and also has an adsorption temperature ranging from 0 to 95 ° C. Desorption temperature can be used in the range of 95 ~ 110 ℃.

The adsorbent according to the present invention uses silica as a support, and since the amount of amine groups is grafted on the surface of the aerogel type silica, the grafting of the aminosilane inside the silica rather than the outer surface of the silica leads to an increase in efficiency. It is efficient to use mesoporous silica.

The amine group grafted on the surface of the silica is most appropriate using an aminosilane group, and since the silicon of the silita and the silicon of the silane group combine to form a strong bond, the decomposition by temperature can be minimized. The adsorbent in which the amine group is present as a functional group in the silica support prepared in this form has a higher adsorption capacity for carbon dioxide than the zeolite molecular sieve, which is the best carbon dioxide adsorbent known to date, at an atmospheric pressure of 50 ° C. or higher. Desorption of carbon dioxide is possible at a lower temperature than the absorbent used, and it can be proposed as an excellent adsorbent for separating carbon dioxide, which occurs at a lower temperature than complete zeolite.

The adsorbent may be used in other fields because an amine group harmless to the human body is present on the surface of silica. For example, the drug component may be covalently bonded to an amine group and used in medicine or cosmetics. The dissolved components can be continuously dissociated and eluted out of the processable silica. The amine group can also be rapidly substituted for use as an adsorbent for catalysts or specific components.

As described above, the present invention is to provide a carbon dioxide adsorbent in which the amine group is present on the silica surface by grafting or coating the amine group on the silica surface,

In another aspect, a solution is prepared by mixing toluene or benzene with any one or more selected from aminotrimethylethoxysilane, aminotriethylmethoxysilane and aminopropyl chloride having an aminosilane group in which an amine group is present, and the solution After the grafted and coated on a silica support, and washing the unreacted amine group, and drying at 100 ~ 120 ℃ after washing may provide carbon dioxide separation, pharmaceutical storage or delivery.

In another aspect, a carbon dioxide separator may be provided by attaching an adsorbent according to the manufacturing process of the present invention to a process of generating carbon dioxide, wherein the carbon dioxide separator is a heat exchanger capable of controlling the temperature of an adsorption tower and an adsorption tower packed with an adsorbent. It is composed of a means to control the flow of carbon dioxide in the desorption tower and the inlet gas containing carbon dioxide in the adsorption tower, and the number of adsorption tower and the pressure controller, flow regulator, and flow controller depending on the purpose. Etc., or may be configured differently.

As described above, the method for preparing an adsorbent having an amine functional group according to the present invention provides an adsorbent having the following effects.

First, the selectivity to carbon dioxide is high, the influence of moisture is low and the adsorption amount is excellent at a higher temperature than the operating temperature of other adsorbents.

In addition, the desorption temperature is lower than that of the absorbent and lower than the desorption temperature of the solid adsorbent. In addition, although the solid adsorbent, most of the separation of carbon dioxide is a chemosorbent in the solid form by absorption by the covalent bond of the amine group and carbon dioxide. Therefore, it is a new concept of solid absorbent which shows chemical absorption and physical adsorption simultaneously.

In addition, when used in the separation process of carbon dioxide can exhibit a high operating effect, it is possible to operate the separation process smoothly and economically by supplementing the disadvantages of the chemical absorption method by the amine and the adsorption method by the solid adsorbent. Therefore, carbon dioxide separation, which is the main culprit of global warming, can be performed, and a smaller indoor application can provide a cleaner indoor environment.

In addition, the adsorbent of the present invention can be used in other fields because of the presence of an amine group harmless to the human body on the surface of silica, for example, it can be widely used as a reservoir of drugs having a slowing effect by covalently binding a drug, cosmetics, etc. to the amine group.

Hereinafter, the above-described technical configuration will be described in more detail with reference to the following examples.

Example 1: Of amine group adsorbent  Produce( Aminopropyltriethoxysilane , MCM -48)

2 g of silica (MCM-48, specific surface area 1012 m 2 / g, pore diameter of 3.1 nm) is vacuum dried. 30cc of anhydrous toluene [Aldrich Chemical, USA] was added to the silica dried in the argon gas atmosphere, and toluene was evenly injected into the pores by using vacuum, and then aminopropyltriethoxysilane [Aldrich Chemical, USA] was added to Pear is added. At room temperature, the mixture was stirred for 6 hours in an argon atmosphere to be evenly dispersed.

This is mounted on a reflux apparatus equipped with a cooler, and the stirring is heated for 12 hours while maintaining the surface temperature of the heater at 150 ° C. After the heating is completed, the resultant is filtered to separate the silica adsorbent grafted with the amine group, the unreacted reactant and the reaction product. The washing is carried out using methyl chloride (Aldrich Chemical, USA) during the separation process. After the washing, the adsorbent separated in the Solex type washer was added, and 100 cc of methyl chloride (Aldrich Chemical, USA) was added, followed by stirring for 3 hours while maintaining the reactor surface temperature at 80 ° C. After stirring is complete, the mixture is washed and filtered using ethyl alcohol [Aldrich Chemical, USA]. The filtered adsorbent is dried for 24 hours at 110 ℃ dryer to completely remove the organic solvent. In this manner, an adsorbent according to the present invention was prepared.

Example 2: Of amine group adsorbent  Produce( Aminopropyltriethoxysilane , MCM -41)

In the same manner as in Example 1, except that the silica was used MCM-41 [Aldrich Chemical, USA] rather than MCM-48.

Example 3 Preparation of Amine Group Adsorbent (Aminopropyltrimethoxysilane, MCM-41)

In the same manner as in Example 1, except that the silica using MCM-41 [Aldrich Chemical, USA], not MCM-48, and instead of the aminopropyltriethoxysilane [Aldrich Chemical, USA] aminopropyltrimethoxy Silane [Aldrich Chemical, USA] was used.

Example 4: Of amine group adsorbent  Produce( Aminopropyltrimethoxysilane , MCM -48)

In the same manner as in Example 1, but instead of the aminopropyltriethoxysilane [Aldrich Chemical, USA] was used aminopropyltrimethoxysilane [Aldrich Chemical, USA].

Example 5: Of amine group adsorbent  Produce( Aminopropyltriethoxysilane , SBA -15)

The same procedure as in Example 1 was carried out, except that SBA-15 [Aldrich Chemical, USA] was used instead of MCM-48.

Test example

After preparing a plurality of fixed bed reactors made of stainless steel (SUS-316) having an inner diameter of 4 mm, the adsorbents prepared in Examples 1 to 5 were installed in the fixed bed reactors, respectively, and the performance of each adsorbent was measured.

The target material carbon dioxide to be adsorbed by the fixed bed reactor was 1.03%, and the feed rate was maintained at 10CC / min.

On the other hand, the experiment was to measure the adsorption amount of carbon dioxide by measuring the concentration of carbon dioxide in the outlet while maintaining the temperature at 75 ℃ while supplying the 1.03% carbon dioxide gas into the fixed bed reactor. The above experiment was performed in the same manner to measure the change in adsorption amount according to the temperature while changing the temperature in the reactor. The result is shown in FIG. And, as shown in Figure 1 it was shown to adsorb a large amount of carbon dioxide.

As described above, those skilled in the art will understand that the present invention may be implemented in other specific forms without changing the technical spirit or essential features of the present invention. Therefore, the exemplary embodiments described above are to be understood in all respects as illustrative and not restrictive.

The scope of the present invention should be construed that all changes or modifications derived from the meaning and scope of the appended claims and equivalent concepts rather than the detailed description are included in the scope of the present invention.

1 is a graph showing the adsorption amount by the covalent bond to the carbon dioxide of the adsorbent according to the present invention.

Claims (4)

A mixing step of mixing 90 to 99 wt% of the silica mixture (A) formed by mixing 0.2 to 50 wt% of silica and 50 to 99.8 wt% of the organic solvent, and 1 to 10 wt% of the material (B) having an amine group; The admixture manufacturing method having an amine functional group, characterized in that consisting of a reaction step of heating the mixture passed through the mixing step at 40 ~ 170 ℃ reacts the amine group with silica and then filtered and washed. The method of claim 1, The organic solvent is any one or two or more selected from toluene, benzene, xylene, hexane, ether, the method for producing an adsorbent having an amine functional group. The method of claim 1, The substance which has an amine group is any 1 type chosen from aminopropylethoxysilane, aminopropylmethoxysilane, and arylamine, The manufacturing method of the adsorbent which has an amine functional group characterized by the above-mentioned. The method of claim 1, Washing in the reaction step is a method for producing an adsorbent having an amine functional group, characterized in that consisting of a washing liquid of any one or two or more selected from ethanol, isopropyl alcohol, methanol, ether, dimethyl chromide, toluene.

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